1. Field of the Invention
The present invention relates to a method of manufacturing a semiconductor device and a substrate processing system.
2. Description of the Related Art
As metal-oxide-semiconductor field effect transistors (MOSFETs) become highly integrated and have high performance, the use of a high permittivity insulation film for gate insulation film is under investigation. In addition, for a capacitor of a dynamic random access memory (DRAM), a high permittivity insulation film such as a HfO2 film or a ZrO2 film having a relative permittivity in the range from, for example, about 15 to about 20 is used. Such a HfO2 film or ZrO2 film can be formed on a substrate accommodated in a processing chamber by alternately repeating a process of supplying a hafnium (He-containing or zirconium (Zr)-containing precursor into the processing chamber and exhausting the precursor from the processing chamber and a process of supplying an oxidizing precursor such as O3 or H2O into the processing chamber and exhausting the oxidizing precursor from the processing chamber while heating the substrate accommodated in the processing chamber to a temperature of 200° C. or higher.
However, if O3 is used as an oxidizing precursor, a metal film such as a bottom electrode disposed under the high permittivity insulation film may be oxidized. In addition, if H2O is used as an oxidizing precursor, OH which has not participated in a reaction may remain in the high permittivity insulation film. To prevent this, a heat treatment process may be performed to modify the high permittivity insulation film; however, in this case, OH remaining in the high permittivity insulation film may be released from the high permittivity insulation film to oxidize the metal film disposed under the high permittivity insulation film. For example, if the metal film is a TiN film, the TiN film may be oxidized to form a TiO(N) layer on the TiN film, and thus the electric capacitance of a capacitor may be reduced. Such problems occur remarkably when the high permittivity insulation film is made of a material having a very high oxygen permeability such as HfO2 or ZrO2 because the diffusion rate of oxygen in HfO2 or ZrO2 is high.